Modified phenolic resins



Patented Oct. 9, 1951 MODIFIED PHENOIJCRESINS Herman S. Bloch, Chicago, Ill., assignor to Universal Oil Products Company, Chicago, 111., a corporation of Delaware No Drawing. Application March 30, 1948, Serial No. 18,072

Claims.

This application is a continuation in part of my co-pending application Serial No. 732,145, filed March 3, 1947, and now abandoned.

The present invention relates to a process for the production of resinous and elastomeric materials characterized herein as modified phenolic resins, the particular modification over the usual phenolic resinous products being the presence of monoand/or polyenic hydrocarbon substituents derivedfrom a specific source of alkenyl and alkapolyenyl hydrocarbon utilized as alkenylating agents of the hydroxy aromatic reactant employed in the preparation of the present resinous product. More specifically, the invention concerns a process for the production of resinous materials by the chemical condensation of a monoor polyalkenyl or alkapolyenyl hydroxy aromatic derivative with a carbonyl compound selected from the group consisting of the aldehydes and ketones.

It is one object of the invention to provide a process for the production of high molecular weight phenolic resins containing unsaturated hydrocarbon radicals which lend particular properties to the resinous product and enable the latter to undergo polymerization and oxidation reactions and to enter into the molecular structure as a copolymer of the drying oil component of coating compositions in which the resin is incorporated when the coating composition is exposed to atmospheric oxygen and undergoes drying as a result thereof.

Another object of the invention is to provide resinous products which are tough, highly elastic and therefore especially desirable in the formulation of coating compositions where such properties are of advantage in increasing the durability and usefulness of coating films derived from such compositions.

In one of its embodiments the present invention comprises reacting a hydroxy aromatic compound containing at least three substitutable nuclear hydrogen atoms with a cyclic polyo1efinic hydrocarbon having conjugated and nonconjugated unsaturation and thereafter condensing the product consisting of monoand poly-alkenyl and alkapolyenyl phenols with a carbonyl compound selected from the group consisting of the aldehydes and ketones to form a resinous material.

In one of its more specific embodiments the present invention relates to a process for the production of a resinous material which comprises reacting a phenol containing at least three substitutable nuclear hydrogen atoms with a mixture of cyclic oleflnic hydrocarbons containing from about 2.5 to about 4 double bonds per molecule in conjugated and non-conjugated relationship to each other to. form a mixture of phenolic compounds containing, in common, monoand polyalkenyl and alkapolyenyl radicals and thereafter condensing said alkenyl phenolic compounds with a carbonyl reactant selected from the group consisting of the aldehydes and ketones in the presence of an acidic condensation catalyst at a temperature of from about 25 to about 200 C. and at a pressure suillcient to maintain the reaction mixture substantially in liquid phase.

Other objects and embodiments of the invention will be referred to in greater detail in the following further description of the invention.

In my co-pendi1.3, parent application hereinabove referred to, the method of preparing one of the primary reactants involved in the present process, the alkenyl and polyalkenyl hydroxy aromatic compounds, such as an alkenvlphenol, has been described with particularity as the reaction of a cyclic polyoleflnic hydrocarbon having conjugated and non-conjugated unsaturation with an hydroxy aromatic compound containing at least one nuclearly substitutable hydrogen atom. The cyclic polyoleflnic hydrocarbon reactant specified in the alkenylation reaction referred to in said process is characterized as the unsaturated hydrocarbon product of a conjunct polymerization reaction in which a non-aromatic hydrocarbon, generally an aliphatic or cyclic monoor polyoleflnic hydrocarbon or branched chain paraflln is contacted with a conjunct polymerization catalyst such as a Friedel- Crafts metal halide or certain concentrated mineral acids such as sulfuric and hydrofluoric acids at temperatures of from about 30 to about 200 C. to form a sludge phase from which said cyclic polyoleflnic hydrocarbons are recovacting said cyclic polyoleflnic hydrocarbons with hydroxy aromatic compounds containing substitutable nuclear hydrogen atoms are herein classed as alkenyl and cycloalkenyl as well as alkapolyenyl derivatives in which a portion of the original unsaturation of the hydrocarbons is retained, thus forming products having from 1 to as high as 3 oleflnic double bonds in the alkenyl substituents. The latter unsaturation is believed to account for the valuable characteristics of the products of this invention in their ability to act as film-forming components in coating compositions in which the present resins 'are incorporated. The interpolymerization effects between the doubly bonded carbon atoms in the structure of the resin may also account for the tough elastic properties of the dried films from such coating compositions, as well as for the enhanced drying speed and certain physical properties of the films such as hardness and abrasion resistance.

The hydroxy aromatic reactant utilized in the formation of the corresponding alkenyl derivatives thereof in accordance with the process of my parent application include not only the monocyclic compounds, that is, the benzenoid or phenolic hydroxy aromatic compounds, but the polycyclic aromatic series as well. Typical compounds of the hydroxy benzenoid series include phenol, the various alkyl and alkenyl derivatives thereof, such as' the. cresols, the polyhydroxy compounds such as resorcinol and phenols containing other substituents such as halogen substituted phenols. In order to form the alkenyl derivatives of said hydroxy aromatic compounds by alkenylation thereof, it is essential that the aromatic nucleus be not substituted by other groups to such an extent that attachment of the alkenyl radical thereto during the alkenylation reaction is prevented by steric hindrance; and the alkenylphenols must be capable of further reaction with carbonyl compounds such as formaldehyde. The hydroxy aromatic compound is therefore specified as containing at least three nuclearly substitutable hydrogen atoms. Of the polycyclic aromatic hydroxy compounds also utiiizable in the alkenylation reaction, typical compounds in this class include the anthrols, phenanthrols and their substitution derivatives such as the hydroxy, halo, alkyl and other substituted polycyclic hydroxyaromatic compounds.

The condensation of the hydroxy aromatic reactant and the polyoleiinic cyclic hydrocarbon mixture to form the corresponding alkenyl hydroxy aromatic derivative is effected in the presence of a suitable catalytic agent of the type generally known to the art as an alkylation catalyst. Typical of such catalysts are the Friedel- Craftsmetal halides such as aluminum chloride, ferric chloride, zinc chloride, etc. the modifled Friedel-Crafts metal halides, for example, one ofthe above metal halides such as stannic chloride dissolved in a suitable solvent, such as a nitro or an addition complex of the halide with various organic compounds such as ethers, esters, ketones, etc. or addition compounds of boron trifluoride with such organic compounds. A typical catalyst of the latter type which is especially desirable in eifecting the alkenylation reaction are the aluminum chloride complexes of certain oxygen-containing organic compounds such as aluminum chloride monomethanolate. Acid earths or clays of either synthetic or natural origin may also be used to catalyze the reaction. Other catalysts utilizablc in the alkenylation reaction are referred to in greater detail in my parent application wherein the preparation of such compounds, utilized herein merely as reactants, is considered specincally.

The formation of the alkenyl hydroxy aromatic compound by alkenylation of a phenol or a polycyclic hydroxy aromatic compound with a cyclic polyoleflnic hydrocarbon. the product of which comprises one of the primary reactants in the present process, may be effected at temperatures of from about 20 to about 200 (7., preferably at temperatures from about 0 to about 125 C. for most of the alkylation catalysts hereinabove specified. Superatmospheric pressures, generally not in excess of about 100 atmospheres, are desirable in the alkenylation reaction to maintain the reactants and catalyst in substantially liquid phase and thereby maintain intimate contact between the reactants. Following the period of reaction in which the alkenyl derivatives of the hydroxy aromatic compound are formed, generally within a reaction period of from about 3 minutes up to about 3 hours, the alkenyl hydroxy I aromatic product may be separated from the resubatmospheric pressures to reduce the boiling point and eliminate thermaldecomposition of the product. The product frequently comprises not only the monoalkenyl and alkapolyenyl substituted derivatives but the diand polyalkenyl derivatives as well. Both the monoand polysubstituted derivatives are utiiizable in the present process to form the resinous product herein provided, although the product obtained from the monoalkenyl derivative usually, but not necessarily, possesses properties differing from the resinous product prepared from a polyalkenyl hydroxy aromatic compound. It has also been observed that the monosubstituted derivatives usually undergo condensation with the carbonyl compound more readily than the polysubstituted compounds, presumably because of the absence of steric hindrance effects; the monoalkenyl derivative is therefore generally preferred in the present process, although the process is not necessarily limited thereto. The polysubstituted hydroxy aromatic compounds are necessarily of higher molecular weight, contain more numerous unsaturated bonds and for these reasons produce harder and in some cases less pli able resinous products. The latter properties are, however, also dependent upon the physical properties and molecular constitution of the carbonyl reactant with which the alkenyl hydroxy aromatic reactant is condensed, the molecular weight and unsaturation thereof as well as the number of substituents in its molecular structure also controlling the properties of the ultimate resinous product.

' The reactant herein specified as a carbonyl compound utilized in the formation of the present resinous product may be an aldehyde or ketone, aliphatic, or cyclic, and of either saturated or unsaturated structure; the cyclic compounds may be either naphthenic or aromatic. Suitable ketones include such saturated members as acetone, methylethyl ketone, diethyl ketone, etc.; cyclic saturated ketones, such as methylcyclohexyl ketone; cyclic members wherein the carbonyl group is part of the ring, such as cyclohexanone; unsaturated ketones, such as vinyl methylketone, ethylideneacetone, mesityl oxide, isophorone, etc.; aryl ketones, such as acetophenone, butyrophenone, benzophenone, etc.; alkenyl arylketones, such as propenyl phenyl ketone; polyketones, such as diacetyl or benzil and' homologs of the above classes. Typical aldehydes of the corresponding classes enumerated above include such compounds as formaldehyde and acetaldehyde of the saturated aliphatic series, crotonaldehyde or acrolein of the unsaturated aliphatic series, benzaldehyde of the aryl aldehydes, and heterocyclic aldehydes such as furfural. The polymers of formaldehyde, such as trioxymethylene are particularly useful since the latter are liquid at relatively high temperatures and depolymerized during the reaction to yield the highly active carbonyl compound. formaldehyde. The aldehydes and ketones may also be employed in admixture with each other or with members of the same "group. The carbonyl reactant may also contain other diverse radicals other than the carbonyl group attached to other carbon atoms in the structure of the compound than the carbonyl carbon atoms, I

thereby introducing various modifications in the properties of the ultimate resinous product. Such other radicals may be one or more of the following group: halogen, nitro, amino, alkoxy. acyloxy, carboxy, carboxamide, or sulfonic acid radicals, which, although they do not enter into the condensation reaction directly with the hydroxy aromatic compound, nevertheless affect the melting point, solubility and other characteristics of the resin. In general, when utilizing an unsaturated carbonyl compound, as for example, the ketone and aldehydes wherein the carbonyl group is attached to an alkenyl residue, the products tend to have somewhat different properties than resins prepared from the correspondin saturated carbonyl reactants containing the same number of carbon atoms. As a rule, the products derived from the unsaturated series of reactants tend to have higher melting points due, it is believed, to incidental polymerization effects obtained between the double bonds of said reactants.

The condensation of a carbonyl reactant selected from the group consisting of the aldehydes and ketones with an alkenyl hydroxy aromatic compound is preferably effected in the presence of certain catalytic agents generally characterized as acid-acting substances. The latter may be selected from either the organic or mineral acids including such acids as acetic, chloroacetic, and oxalic acids, various sulfonic acids, such as ethanesulfonic acid, etc. of the former class and hydrochloric, sulfuric, phosphoric, etc. acids of the mineral acid class of catalyts. The catalyst is introduced into the reaction mixture in sumcient quantity to result in a slightly acidic reaction mixture, generally in amounts of from about 0.1 to about weight per cent of the reaction mixture. When utilizing mineral acid catalysts, the quantity of catalyst is generally less than about 5%, whereas organic acids may be present in amounts up to about 10% of the reaction mixture. The catalyst may be subsequently removed from the resinous product by contacting the resinous reaction mixture with a solOent which has a selective solubility for the catalyst, such as water containing a base or alkali, or the resin may be dissolved away from the catalyst, as for example, by contacting the resin containing the' catalyst with a hydrocarbon such as benzene which dissolves thew resinbut not the catalyst. l

The condensation-reaction may be conducted in the presence of a solvent for the reactants, the solvent tending to modify the rate of reaction and the character of the products obtained therefrom. In general, the aliphatic alcohols such as butyl alcohol, ethers'such as diethylether,esters, such as ethylacetate and hydrocarbon solvents suchas benzene, toluene, etc. provide suitable solvents or diluents in which to conduct the reaction. The solvent may be added for the specific purpose of controlling the rate of reaction, as for example, where a solvent is chosen which vaporizes at the reaction temperature and thus maintains its temperature at the boiling point of the solvent. The solvent may also form an azeotrope with the byproduct water formed in the reaction and thus provide an effective means for removing the latter undesirable product from the reactionmixture.

The resin-formingreaction of the present process may be effected at temperatures of from about 25 to about 200 C. and preferablyfrom about 40 to about C. and at pressures sufllcient to maintain the reactants in substantially liquid phase. The proportion of carbonyl compound to alkenyl hydroxy aromatic compound utilized in the reaction mixture may vary from about 0.5 to about 2 molecular proportions thereof. It is generally preferred to maintain the molecular ratio of carbonyl compound to alkenyl hydroxy aromatic reactant within the range of from about 0.7 to about 1.2 as the resinous products obtained thereby generally possess'more of the desirable characteristics of such resins. In general. lowering said above ratio results in the production of a soft resinous material whereas increasing the ratio tends to produce resins of hard, brittle characteristics. Within the range specified, the resins may vary from soft resins or fluid resinoids to hard, tough, elastic products, depending upon the degree of condensation desired for the particular use intended. -In either case, the resins possess the ability to condense and polymerize further by the action of heat and pressure with or without polymerization catalysts such as peroxides, organic acids, or acid-acting salts like zinc chloride.

The residual unsaturation contained in the resinous products is believed to account for the ability of the resins to undergo further polymerization under the influence of heat and pressure, etc. For similar reasons, the products may be vulcanized in the presence of sulfur when subjected to heat, pressure and in the presence of suitable accelerators. Because of the unusual combination of properties found in the present resinous products, they should find wide use as molding materials, coatings, rubber additives, adhesives and impregnants for cloth, wood and paper, as for example in the manufacture of laminated products. The quality of the resins may be varied within wide limits to secure products of almost anyspecifled properties varying These may be blended in the flnished state or the aldehyde reaction may be carried out on a mixture of the alkenyl hydroxy aromatic compound with other substituted phenols or 'with urea, thio-urea, melamine. amino-sulfonamides and like materials capable of forming resinous condensation products with aldehydes.

The present invention is further illustrated and typical products obtained by means of the present process are characterized in the following examples wherein certain members of the generally broad classes of reactants, catalysts and reaction conditions are specifled for the purpose of indicating the method of obtaining the present resinous product, but not with any intention of limiting the generally broad scope of the invention in accordance therewith.

Example I A mixture of polyoleflnic cyclic hydrocarbons containing conjugated and non-coniugated unsaturation, also hereinabove characterized as conjunct polymers, was prepared in accordance with the following procedure.

22 liters (16.5 kg.) of non-selective-copolymer hydrocarbons having a bromine number of 162 (polymers of mixed butylenes and propylene referred to as a polymer gasoline) consisting predominantly of mono-oleflnic hydrocarbons containing from about 8 to about 12 carbon atoms per molecule was charged into an autoclave and rapidly stirred as 9.0 kg. of liquid anhydrous hydrogen fluoride was introduced into the reactor. The pressure was maintained throughout the reaction at an average value of about 205 pounds per square inch by means of compressed nitrogen. The temperature was increased to 91 C. and stirring was continued for an additional hour. The reaction mixture separated into two phases on standing; an upper saturated hydrocarbon layer (bromine number=l0) and a lower acidic sludge layer.

The lower layer product weighed 16.1 kg. after removal of entrained "upper layer by extracting the latter with liquid pentane and was a light Boiling range ltoabove 400 C. Density, d4 0.863 Molecular weight, average 263 Diene number Bromine number 195 Double bonds/molecule (average) 8.2

Although the mixture of polyoleflnic cyclic hydrocarbohs described in the above preparation was prepared from a hydrogen fluoride sludge and was recovered therefrom by an aqueous hydrolysis procedure, a somewhat similar material may be obtained from an aluminum chloride of sulfuric acid sludge prepared in similar fashion. The polyoleflnic cyclic hydrocarbons may also be recovered from the hydrogen fluoride sludge by methods other than the aqueous hydrolyzing procedure. For example, the sludge may be catalytically decomposed by vaporizing the hydrogen 7 fluoride from the sludge in the-presence of certain catalysts, depositing the hydrocarbons as a residue thereof.

The mixture of polyoleflnic cyclic hydrocarbons obtained in the above coniunct polymerisation reaction was fractionally distilled at a subatmospheric pressure (5 mm. Hg, absolute) to separate a fraction therefrom boiling from about 200 to about 275 0., the hydrocarbons therein having an average molecular weight of about 1'16. 0.275 mol of the latter fraction and a molar equivalent (26 grams) of phenol were weighed into a tared three-neck flask, immersed into an .oil bath, swept out with nitrogen and stirred while heating to about C. To this mixture was added dropwise while stirring was continued, approximately 10 weight-percent of the reaction mixture of a liquid catalyst consisting of a boron trifluorlde-diethylether complex. The reaction was allowed to continue for flve hours; the mixture was then allowed to cool to room temperature and washed with a dilute solution of sodium carbonate to remove the catalyst component. The product was dried over sodium sulfate and distilled at a pressure of 5 mm. Hg absolute. The yield of alkenyl phenols obtained from the above alkenylation reaction was ap-' proximately 81.2%, based on the weight of reactants involved. A monoalkenyl fraction boilin: from about 358 to about 400 C. (at 160 mm. prasure) was separated and utilized for the subsequent condensation reaction to form a resinous product.

1.0 mol of the monoalkenylated phenol product is admixed with trioxymethylene in an amount suflicient to provide a molar equivalent of formaldehyde in the reaction mixture. To this mixture is added 1% by weight thereof of oxalic acid catalyst and the resulting mixture heated to a temperature of approximately 55 C. A viscous reaction product is soon formed which on further reaction at the indicated conditions forms a flexible resinous mass having rubber-like properties. The product is subject to vulcanization and consequent hardening by incorporating from 1 to 10% by weight of sulfur therein and heating under pressure at a temperature of 0.

Example 11' the phosphoric acid catalyst from the reaction I mixture and the dried toluene solution evaporated to recover the resinous product.

I claim as my invention:

l. A process for the production of a resinous 78 product which comprises reacting a mixture of hydrogen atoms with a mixture of cyclic polyoleflnic hydrocarbons having conjugated and non-conjugated unsaturation in the same molecule.

2. A process for the production of a resinous product which comprises reacting a mixture of monoand poly-alkenyl and alkapolyenyl phenols with a carbonyl compound selected from the group consisting of the aldehydes and ketones in the presence of an acidic condensation catalyst at a temperature of from about 40 C. to about 125 C. and in the molecular ratio of said carbonyl compound to said phenols of from about 0.7 to about 1.2, said phenols being the condensation product of a hydroxy aromatic compound containing at least three substitutable nuclear hydrogen atoms with a mixture of cyclic polyolefinic hydrocarbons having conjugated and 10 non-conjugated unsaturation in the same molecule.

3. The process of claim 1 further characterized in that said alkenyl and alkapolyenyl phenols and said carbonyl compound are reacted in the presence of oxalic acid as said condensation catalyst.

4. The process of claim 1 further characterized in that said carbonyl compound is formaldehyde.

5. The resinous product formed by the process of claim 1.

HERMAN S. BLOCK.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,101,853 Harvey Dec. 14, 1937 2,114,121 Bender Apr. 12, 1938 2,154,192 Zinke Apr. 11, 1939 2,162,172 Honel June 13, 1939 2,329,397 DO'uville et al. Sept. 14, 1943 2,343,296 Honel Mar. 7, 1944 2,400,521 -Kuhn Jr. May 21, 1946 2,423,415 Soday July 1, 1947 2,470,894 Johnstone May 24, 1949 

1. A PROCESS FOR THE PRODUCTION OF A RESINOUS PRODUCT WHICH COMPRISES REACTING A MIXTURE OF MONO- AND POLY-ALKENYL AND ALKAPOLYENYL PHENOLS WITH A CARBONYL COMPOUND SELECTED FROM THE GROUP CONSISTING OF THE ALDEHYDES AND KETONES IN THE PRESENCE OF AN ACIDIC CONDENSATION CATALYST AT A TEMPERATURE OF FROM ABOUT 25* C. TO ABOUT 200* C. AND IN THE MOLECULAR RATIO OF SAID CARBONYL COMPOUND TO SAID PHENOLS OF FROM ABOUT 0.5 TO ABOUT 2, SAID PHENOLS BEING THE CONDENSATION PRODUCT OF A HYDROXY AROMATIC COMPOUND CONTAINING AT LEAST THREE SUBSTITUTABLE NUCLEAR HYDROGEN ATOMS WITH A MIXTURE OF CYCLI POLYOLEFINIC HYDROCARBONS HAVING CONJUGATED AND NON-CONJUGATED UNSATURATION IN THE SAME MOLECULE. 